Sciencemadness Discussion Board - Cheapest Hydroxylamine

Cheapest Hydroxylamine

TEK - 4-8-2009 at 15:47

What place has the cheapest hydroxylamine hcl? If anyone on here wants to sell any send me a U2U.

[Edited on 4-8-2009 by TEK]

Formula409 - 5-8-2009 at 01:35

Considered http://www.sciencemadness.org/member_publications/energetic_... ?

Formula409.

Siddy - 21-8-2009 at 15:58

Is there away to easily separate the formic acid from that mix?

Saturate with hydroxide salt and boil/evap hydroxylamine (decomp) and water?

Picric-A - 22-8-2009 at 13:05

add to water to crystalise out the salt crystals

Siddy - 23-8-2009 at 00:08

how, when formate salts are typically VERY soluble?

starman - 14-9-2009 at 17:54

Hydroxylamine can also be produced by the reduction of nitrous acid or potassium nitrate with bisulfite:

HNO2 + 2 HSO3− → N(OH)(OSO2)22− + H2O → NH(OH)(OSO2)− + HSO4−
NH(OH)(OSO2)− + H3O+ (100 °C/1 h) → NH3(OH)+ + HSO4−

I was wondering if anyone had come across a detailed preparation of this route.

ammonium isocyanate - 14-9-2009 at 18:44

You can get it at http://www.photoformulary.com/DesktopDefault.aspxtabindex=2&... but at 16.25 for 100g it's not exactly cheap but not too bad either. Not sure what their shipping policy is though.

S.C. Wack - 14-9-2009 at 18:50

Quote: Originally posted by starman

Hydroxylamine can also be produced by the reduction of nitrous acid or potassium nitrate

Nitrate = fail
Brauer = win (a useful potassium salt).

Formula409 - 14-9-2009 at 18:55

Quote: Originally posted by starman

I was wondering if anyone had come across a detailed preparation of this route.

Here we go:
http://www.erowid.org/archive/rhodium/chemistry/hydroxylamin...
http://www.orgsyn.org/orgsyn/prep.asp?prep=cv1p0318

Formula409.

S.C. Wack - 14-9-2009 at 19:22

He used the word bisulfite and I assumed that this meant bisulfite, the actual salt; not in situ - which are a dime a dozen in the literature.

Sedit - 14-9-2009 at 19:36

The second reference in the paper is stated to use Sodium Bisulfite and Sodium Nitrite solutions S.C.

Reference: Raschig, Ann. 241, 161 (1887); Ger. pat. 41,987 [Chem. Zentr. I, 246 (1888)]; Divers and Haga, J. Chem. Soc. 69, 1665 (1896); 77, 673 (1900); Adams and Kamm, J. Am. Chem. Soc. 40, 1281 (1918).

The other reference Raschig, Ger. pat. 216,747 [Chem. Zentr. I, 308 (1910)] is mentioned to use Calcium nitrite inorder to precipitate the formed Calcium Sulfate from the solution with ease.

Im going to attempt to find these papers as I have the desire to attempt the former process and see how effective it is.

S.C. Wack - 15-9-2009 at 13:16

Quote: Originally posted by Sedit

The second reference in the paper is stated to use Sodium Bisulfite and Sodium Nitrite solutions S.C.

Yeah I can read, and am aware of this "Organic Syntheses" thing. The only one of those that actually has a procedure for using solid bisulfite, is Rachig...and guess whose article is translated to English in Brauer. I tend to write with care.

I was just trying to point out that all other literature procedures make sodium bisulfite, while the one in Brauer uses it.

Sedit - 15-9-2009 at 13:37

My fault, I thought you where making mention to looking for one that uses the salt instead of insitu production. You don't by anychance have that paper on hand do you since I am quite interested in seeing some experimental details of it. I have not had the time to look for it just yet but will do so in a bit.

starman - 15-9-2009 at 16:53

mmm - Interesting gentlemen.Just happen to have some calciuim nitrite,but not access to Brauer. I think I'll take a peek at the DE patent.

entropy51 - 15-9-2009 at 17:24

Quote: Originally posted by starman

mmm - Interesting gentlemen.Just happen to have some calciuim nitrite,but not access to Brauer. I think I'll take a peek at the DE patent.

Isn't Brauer in the Forum library????

DJF90 - 15-9-2009 at 19:08

Yup.

starman - 15-9-2009 at 20:20

Whoops. I'm going to translate the example section of the DE patent anyways.Dust off the high school german.

EmmisonJ - 3-10-2009 at 15:01

Quote: Originally posted by ammonium isocyanate

You can get it at http://www.photoformulary.com/DesktopDefault.aspxtabindex=2&... but at 16.25 for 100g it's not exactly cheap but not too bad either. Not sure what their shipping policy is though.

they sell the sulfate but he's looking for the hcl salt. wouldn't it be easier to do like ammonium isocyanate says and buy the sulfate then convert it to the hcl salt? i'm not too familiar with hydroxylamine i'm curious if a simple a/b would work? not sure about it's solubility in water in these various salt forms. it also seems that it's pretty volatile and would melt into a gas at a few degrees above room temp. it would probably be best to play on its solubility to keep it solvated throughout the process. does anyone know a good way to go about converting the sulfate to the hcl salt in this case?

[Edited on 3-10-2009 by EmmisonJ]

Theophrastus_2 - 6-10-2009 at 14:25

Actually, I know that some stores sell racing fuel for cars, that is composed purely of nitromethane, solvated in methanol, and costs something around $16 per Litre (/ 1.5 litres; I'm not exactly sure). Addition of hydrochloric acid to the nitromethane solution, would then give you the intended hydroxylamine hydrochloride. Out of interest, I'm pretty sure that formic acid would be miscible with methanol, but how soluble in contrast, is hydroxylamine hydrochloride in methanol? I sometimes use good amounts of miscible organics, in order to precipitate and induce crystalization in substances, however, I've only used acetone yet. When I get some racing fuel, I'll see how I'll have to extract the hydroxylamine hydrochloride, but as I said, that may take a fair while. Until then, does anyone have some empirical evidence on the matter? -Theo

UnintentionalChaos - 6-10-2009 at 15:34

Quote: Originally posted by Theophrastus_2

Actually, I know that some stores sell racing fuel for cars, that is composed purely of nitromethane, solvated in methanol, and costs something around $16 per Litre (/ 1.5 litres; I'm not exactly sure). Addition of hydrochloric acid to the nitromethane solution, would then give you the intended hydroxylamine hydrochloride. Out of interest, I'm pretty sure that formic acid would be miscible with methanol, but how soluble in contrast, is hydroxylamine hydrochloride in methanol? I sometimes use good amounts of miscible organics, in order to precipitate and induce crystalization in substances, however, I've only used acetone yet. When I get some racing fuel, I'll see how I'll have to extract the hydroxylamine hydrochloride, but as I said, that may take a fair while. Until then, does anyone have some empirical evidence on the matter? -Theo

One of the published procedures we have here details a simple pressure reactor to carry out hydrolysis of nitromethane. I'm under the impression that it does not proceed readily at room temp or even reflux.

benzylchloride1 - 6-10-2009 at 20:24

I na synthesis of dimethylglyoxime, I produced a solution of hydroxylamine in water by reacting sodium bisulfite with sodium nitrite in a slightly acid ic solution. The solution turns quite dark in color and the temperature has to be carefully controlled. The biacetyl monoxime is then added to the hydroxylamine solution and the mixture was brought to a boil and filtered. After cooling for several hours in an ice bath, large quantities of dimethylglyoxime formed. This was filtered off and dried. The product melted at 245 degrees Celsius and was obtained in a yeild of around 40% based on 2-butanone. This procedure was adapted from Vogel and Organic Syntheses. This should be applicable to water soluble ketones. I have tired to synthesize hydroxylamine hydrochloride several times with little success. The hydroxylamine hydrochloride could be obtained from the solution by forming acetoxime with acetone, steam distilling the oxime, hydrolyzing the oxime with hydrochloric acid and then concentration to obtain the hydroxylamine hydrochloride.

Picric-A - 7-10-2009 at 10:28

Must you use an exess of bisulphite becuase hydroxylamine reacts with sodium nitrite releasing nitrous oxide

starman - 7-10-2009 at 21:40

Quote: Originally posted by EmmisonJ

Quote: Originally posted by ammonium isocyanate

You can get it at http://www.photoformulary.com/DesktopDefault.aspxtabindex=2&... but at 16.25 for 100g it's not exactly cheap but not too bad either. Not sure what their shipping policy is though.

Use calcium chloride for a simple displacement,precipitating calcium sulfate.Purification can make use of the fact that hydroxylamine HCl is far more soluble in organic solvents than the sulfate.

EmmisonJ - 2-12-2009 at 07:47

i've read a few different msds but was curious on a couple practical aspects of hydroxylamine. it seems that hydroxylamine isn't alarmingly toxic, but it is explosive and that is really the only concern with handling it but that is in reference to the freebase form.

1. what about how explosive is the salt form? any other concerns?
2. also what about proper storage of the hcl salt form? basically two choices for storage are available - a non-air-conditioned room that gets 100+F in the summer or in the freezer.
3. how long can hydroxylamine hcl be stored without worry about decomposition? is it like hydroquinone and MeAm HCl in the sense that if stored properly they will basically be fine for decades? i see it's hygroscopic and must be kept dry and also must not get heated to its decomposition temp of ~155C (or 17C when dissolved in water, apparently it decomposes readily in water?)

Arrhenius - 2-12-2009 at 19:28

1.) Its salt is definitely safe to work with, unless you want to heat it dry or perhaps with a flame (both general no-no's anyway).
2.) Doesn't matter. Just don't open hygroscopic reagents while the bottle's still cold (condenses water).
3.) Quite a long time. Ammonium salts (hydrochlorides especially) are not prone to oxidation, and thus can be stored almost indefinitely. And it doesn't decompose 'readily' in water. Most reactions involving hydroxylamine, however, are nonetheless not carried out in water.

I would consider it comparable to ammonium chloride. Nothing to be overly concerned about. Since you can't really buy hydroxylamine free-base, and you generally make it <i>in situ</i> it's really not a cause for concern. Explosive and flammable things are (generally) well behaved in solution.

Organikum - 20-12-2022 at 14:29

Tired of wasting Nitromethane for making Hydroxylamine I got myself a big bag of Sodium Nitrite and had an astonishing hard time to find the related simple method for making the Amine from Nitrite and Bisulfite.

Everybody mentions it but nobody just links or quotes it.

Here we go:
From Brauers in the SCM library page 503

Quote:

Potassium Hydroxylamine Disulfonate
HON(SO3K)2
NaNO2 + 2NaHSO3 = HON(SO3Na)2 + NaOH
69.0 208.1 237.1 40.0
A solution of 69 g. of NaNO3 in the minimal quantity of water
is prepared and mixed with 200 g. of ice. A cooled solution of NaHSO3, prepared either by dissolving 208 g. in the minimal quantity of water or by dissolving the same quantity in 600 ml. of technical (35%) bisulfite solution, is added in portions with agitation.
Ice should still be present at the end of the addition. A cold, saturated solution of 150 g. of KCl is then added and the reaction mixture is left to stand for 24 hours. Half of the theoretical yield of disulfonate separates as compact crystals together with fine needles of trisulfonate. The nitrilotrisulfonate can be easily removed by washing and decantation. The HON(SO3K)3 is then recrystallized from a small amount of hot water to which some KOH or ammonia is added (a few seed crystals are retained for this purpose from the first crystallization because the salt tends to form supersaturated solutions).

In another procedure, one mole of KNO2 and 1.1-1.2 moles of
potassium acetate are dissolved in 200 ml. of ice water; 1500 g. of
finely shaved ice is added and SO3 is bubbled through the agitated
reaction mixture until the solution gives the characteristic odor of the gas. The temperature may not exceed 0°C. The disulfonate formed may be washed with a small amount of water and recrystallized as above.

PROPERTIES:
Formula weight 269.35. Hard, shiny crystals, which readily decompose to K2SO4 and hydroxylamine on boiling with water.

REFERENCES:
F. Raschig, Lieb. Ann. Chem. 241^, 183 (1887).
G. K. Rollefson and C. F. Oldershaw, J. Amer. Chem. Soc. 54, 977
81932).

The second attached article contains the IMHO best way to prepare Hydroxylamine as it uses only the more common Sodium Nitrite, the abundant Sodium Meta Bisulfite, HCl and Alcohol to yield the HCl salt of Hydroxylamine.

regards
/ORG

Attachment: phpKGYzJS (197kB)
This file has been downloaded 204 times

Attachment: hydroxylamine_nitrit sulfit.djvu (135kB)
This file has been downloaded 235 times

clearly_not_atara - 21-12-2022 at 13:52

Quote:

and SO3 is bubbled through the agitated
reaction mixture

Surely he means to say "and SO2 is bubbled..."

Organikum - 26-12-2022 at 23:42

Quote: Originally posted by clearly_not_atara

Quote:

and SO3 is bubbled through the agitated
reaction mixture

Surely he means to say "and SO2 is bubbled..."

You are right, SO2, the OCR on the document is horrible, I fixed most before posting it but I must have overlooked this one. Thx. for pointing it out.

regards
/ORG

Dr.Bob - 27-12-2022 at 17:31

And Hydroxylamine HCl is quite stable to store, used it for a few reactions, easy to free base when needed or just react along with one eq of TEA or Hunig's base. Or it can react with carbonyls as the salt, then reduce with NaCNBH3 to make alkyl hydroylamines. Used in many metal chelators.

Fery - 1-1-2023 at 09:40

Hi Organikum, the cheapest way is to buy the hydroxylamine hydrochloride or sulfate.
https://chemcraft.su/search/node/hydroxylamine
How much do you need? I have few very old jars (few decades old), it reacted well.

Lionel Spanner - 9-1-2023 at 10:04

I recently tried the first method in Brauer, and found it reliably reproducable. The only difference is that I went via sodium hydroxylamine disulphonate (didn't have any potassium chloride), and ended up with a lower yield - 36% as opposed to 50%.

The sulphonate salt can then be converted to hydroxylamine sulphate in near-quantitative yields simply by refluxing for 4 hours (Brauer p. 499).